Millimeter-Wave Spectroscopy of Methylfuran Isomers: Local vs. Global Treatments of the Internal Rotation
Methylfurans are methylated aromatic heterocyclic volatile organic compounds and primary or secondary pollutants in the atmosphere due to their capability to form secondary organic aerosols in presence of atmospheric oxidants. There is therefore a significant interest to monitor these molecules in t...
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MDPI AG
2022-06-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/11/3591 |
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| author | Jonas Bruckhuisen Sathapana Chawananon Isabelle Kleiner Anthony Roucou Guillaume Dhont Colwyn Bracquart Pierre Asselin Arnaud Cuisset |
| author_facet | Jonas Bruckhuisen Sathapana Chawananon Isabelle Kleiner Anthony Roucou Guillaume Dhont Colwyn Bracquart Pierre Asselin Arnaud Cuisset |
| author_sort | Jonas Bruckhuisen |
| collection | DOAJ |
| description | Methylfurans are methylated aromatic heterocyclic volatile organic compounds and primary or secondary pollutants in the atmosphere due to their capability to form secondary organic aerosols in presence of atmospheric oxidants. There is therefore a significant interest to monitor these molecules in the gas phase. High resolution spectroscopic studies of methylated furan compounds are generally limited to pure rotational spectroscopy in the vibrational ground state. This lack of results might be explained by the difficulties arisen from the internal rotation of the methyl group inducing non-trivial patterns in the rotational spectra. In this study, we discuss the benefits to assign the mm-wave rotational-torsional spectra of methylfuran with the global approach of the <i>BELGI</i>-C<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mi>s</mi></msub></semantics></math></inline-formula> code compared to local approaches such as XIAM and ERHAM. The global approach reproduces the observed rotational lines of 2-methylfuran and 3-methylfuran in the mm-wave region at the experimental accuracy for the ground v<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow></mrow><mi>t</mi></msub><mo>=</mo><mn>0</mn></mrow></semantics></math></inline-formula> and the first torsional v<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow></mrow><mi>t</mi></msub><mo>=</mo><mn>1</mn></mrow></semantics></math></inline-formula> states with a unique set of molecular parameters. In addition, the <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>V</mi><mn>3</mn></msub></semantics></math></inline-formula> and <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>V</mi><mn>6</mn></msub></semantics></math></inline-formula> parameters describing the internal rotation potential barrier may be determined with a high degree of accuracy with the global approach. Finally, a discussion with other heterocyclic compounds enables the study of the influence of the electronic environment on the hindered rotation of the methyl group. |
| first_indexed | 2024-03-10T01:03:59Z |
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| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T01:03:59Z |
| publishDate | 2022-06-01 |
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| series | Molecules |
| spelling | doaj.art-f22ed972a79e45c298a688c722f677532023-11-23T14:31:12ZengMDPI AGMolecules1420-30492022-06-012711359110.3390/molecules27113591Millimeter-Wave Spectroscopy of Methylfuran Isomers: Local vs. Global Treatments of the Internal RotationJonas Bruckhuisen0Sathapana Chawananon1Isabelle Kleiner2Anthony Roucou3Guillaume Dhont4Colwyn Bracquart5Pierre Asselin6Arnaud Cuisset7LPCA, Laboratoire de Physico-Chimie de l’Atmosphère, Université du Littoral Côte d’Opale, UR4493, F-59140 Dunkerque, FranceCNRS, MONARIS, UMR8233, Sorbonne gé, 4 Pl Jussieu, F-75005 Paris, FranceCNRS UMR 7583, Laboratoire Interuniversitaire des Systèmes Atmosphériques, Université Paris Cité and Université Paris Est Créteil, F-75013 Paris, FranceLPCA, Laboratoire de Physico-Chimie de l’Atmosphère, Université du Littoral Côte d’Opale, UR4493, F-59140 Dunkerque, FranceLPCA, Laboratoire de Physico-Chimie de l’Atmosphère, Université du Littoral Côte d’Opale, UR4493, F-59140 Dunkerque, FranceLPCA, Laboratoire de Physico-Chimie de l’Atmosphère, Université du Littoral Côte d’Opale, UR4493, F-59140 Dunkerque, FranceCNRS, MONARIS, UMR8233, Sorbonne gé, 4 Pl Jussieu, F-75005 Paris, FranceLPCA, Laboratoire de Physico-Chimie de l’Atmosphère, Université du Littoral Côte d’Opale, UR4493, F-59140 Dunkerque, FranceMethylfurans are methylated aromatic heterocyclic volatile organic compounds and primary or secondary pollutants in the atmosphere due to their capability to form secondary organic aerosols in presence of atmospheric oxidants. There is therefore a significant interest to monitor these molecules in the gas phase. High resolution spectroscopic studies of methylated furan compounds are generally limited to pure rotational spectroscopy in the vibrational ground state. This lack of results might be explained by the difficulties arisen from the internal rotation of the methyl group inducing non-trivial patterns in the rotational spectra. In this study, we discuss the benefits to assign the mm-wave rotational-torsional spectra of methylfuran with the global approach of the <i>BELGI</i>-C<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mi>s</mi></msub></semantics></math></inline-formula> code compared to local approaches such as XIAM and ERHAM. The global approach reproduces the observed rotational lines of 2-methylfuran and 3-methylfuran in the mm-wave region at the experimental accuracy for the ground v<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow></mrow><mi>t</mi></msub><mo>=</mo><mn>0</mn></mrow></semantics></math></inline-formula> and the first torsional v<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msub><mrow></mrow><mi>t</mi></msub><mo>=</mo><mn>1</mn></mrow></semantics></math></inline-formula> states with a unique set of molecular parameters. In addition, the <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>V</mi><mn>3</mn></msub></semantics></math></inline-formula> and <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>V</mi><mn>6</mn></msub></semantics></math></inline-formula> parameters describing the internal rotation potential barrier may be determined with a high degree of accuracy with the global approach. Finally, a discussion with other heterocyclic compounds enables the study of the influence of the electronic environment on the hindered rotation of the methyl group.https://www.mdpi.com/1420-3049/27/11/3591methylfuranmm-wave spectroscopyinternal rotationexcited torsional stateslocal vs. global approaches |
| spellingShingle | Jonas Bruckhuisen Sathapana Chawananon Isabelle Kleiner Anthony Roucou Guillaume Dhont Colwyn Bracquart Pierre Asselin Arnaud Cuisset Millimeter-Wave Spectroscopy of Methylfuran Isomers: Local vs. Global Treatments of the Internal Rotation Molecules methylfuran mm-wave spectroscopy internal rotation excited torsional states local vs. global approaches |
| title | Millimeter-Wave Spectroscopy of Methylfuran Isomers: Local vs. Global Treatments of the Internal Rotation |
| title_full | Millimeter-Wave Spectroscopy of Methylfuran Isomers: Local vs. Global Treatments of the Internal Rotation |
| title_fullStr | Millimeter-Wave Spectroscopy of Methylfuran Isomers: Local vs. Global Treatments of the Internal Rotation |
| title_full_unstemmed | Millimeter-Wave Spectroscopy of Methylfuran Isomers: Local vs. Global Treatments of the Internal Rotation |
| title_short | Millimeter-Wave Spectroscopy of Methylfuran Isomers: Local vs. Global Treatments of the Internal Rotation |
| title_sort | millimeter wave spectroscopy of methylfuran isomers local vs global treatments of the internal rotation |
| topic | methylfuran mm-wave spectroscopy internal rotation excited torsional states local vs. global approaches |
| url | https://www.mdpi.com/1420-3049/27/11/3591 |
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